Merocyanine dyes containing a carboxyalkyl group or a sulfoalkyl group



Patented Aug. 15, 1950 MEROCYANINE DYES CONTAINING A CAR- BOXYALKYL GROUP on A SULFOALKYL GROUP I Robert H. Sprague, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New J ersey,

No Drawing. Application February 24, 1947,

' Serial No. 730,565

g 1 9 Claims.

,1 This invention relates to merocyanine dyes containing a carboxyalkyl or a sulfoalkyl group on the nitrogen atom of the auxochromophore group.

In merocyanine dyes the auxochromophore group consists of a nitrogen atom (contained in a heterocyclic ring) linked by a conjugated chain of carbon atoms to the oxygen atom of a keto group (i. e. a carbonyl group) which is usually contained in a heterocyclic ring. Merocyanine dyes containing a methyl, an ethyl, an allyl, a benzyl, a fi-ethoxyethyl, a p-hydroxyethyl and other alcohol radicals on the nitrogen atom of the auxochromophore group are known.- Such known merocyanine'dyes are, generally speaking, neutral substances having a tendency to exhibit basic properties.

I have now found a new group of merocyanine dyes which are acidic and which behave in a manner different from the known merocyanine dyes when photographic silver halide emulsions containing them areprocessed. My new dyes, like the known merocyanine dyes, sensitize photographic silver halide emulsions I have found, but unlike the known merocyanine dyes are substantiall removed from the emulsions upon processing in the ordinary alkaline developers, with the result that photographic elements comprising the silver halide emulsions do not carry a residual dye-stain. A few of my new dyes aredevoid of Qi wherein R represents a member selected from the group consisting of carboxyalkyl and sulfoalkyl groups (e. g. a carboxymethyl group, a 3- carboxyethyl group, an a-carboxyethyl group, an

c,' -dicarboxypropyl group, a sulfomethyl' group,

A further obboxyethylrhodanine,

" done nuclei,

a fl-sulfoethyl group, etc.), L represents a. methine group, n represents a positive integer of from 1 to 2, m represents a positiv integer of from l to 4, Q1 represents a member selected from the group consisting of an oxygen atom, a sulfur atom and a group wherein R2 represents a member selected vclic-nucleus containing from 5 to 6 atoms in the ring. Exemplary of heterocyclic nuclei containing from 5 to 6 atoms in the ring are: rhodanine nuclei (e. g. unsubstituted rhodanine, 3-ethylrhodanine, 3-p-hydroxyethylrhodanine, 3-carboxymethylrhodanine, 3-p-sulfoethylrhodanine, 3- (1,3 -dicarboxy-n-propyl) rhodanine, 3-a-car- S-p-carboxyphenylrhodanine, 3-(3-carboxy-4-hydroxyphenyl) rhodanine, 3-p-sulfophenylrhodanine, 3- (2,5-disulfophenyl) rhodanine, B-phenylrhodanine, 3-p-dimethylunsubstituted 2-thiohydantoin, 1,3-diphenyl-2- thiohydantoin, 3 ethyl-1-phenyl-2-thiohydantoin, l-methyl-Z-thiohydantoin, l-carboxymethyl-3-phenyl-2-thiohydantoin, etc.), B-pyrazolone nuclei (e. g. 1-phenyl-3-methyl5-pyrazolone, 3- methyl-1-(2 benzothiazolyl)-5-pyrazolone, 3- carboxymethyl 1 phenyl-E-pyrazolone, l-carboxyphenyl-S-methyl 5-pyrazolone, B-methyl-l- Y p-sulfophenyl-5pyrazolone, 1- (4-sulfo-1-naphthyl) -3-methyl-5-pyrazo1one, etc), 4-thiazoli- 2-amin0-4(5) -thiazolone nuclei '(e. g. 2-diphenylamino-4(5)thiazolone, Z-dieth- -ylamino-4(5) thiazolone, etc.) Z-alkylmercapto- 3 4-(5)thiazolone (e. g. 2-methylmercapto-4(5)- thiazolone, 2-ethylmercapto-4 (5) thiazole, etc.) barbituric acid nuclei (e. g. unsubstituted barbituric acid, Z-thiobarbituric acid, etc.) and the like. Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 carbon atoms in the heterocyclic ring, e. g. a nucleus of the benzoxazole series (e. g. benzoxazole, 5-chlorobenzoxazole, 5- broinobenzoxazole, o-methylbenzoxazole- 5-ethylbenzoxa'z'o'le, 5-mthoxybenzokazole, 5-ethoxybenzoxazole, 5-acetaminobenzoxazole, 5-phenylbenzoxazole, fi-chlorobenzoxazole, '7-chlorobenzoxazole, etc.), a nucleus of the benzothiazo le series (e. g. benzothiazole, 4-'cholorobenz'thiazole; 'Z-chlorobenzothiazole, 5-chlor6bh'z othiazole, 4'- phenylbenzothiazole, i-methoxybenzothiaz ole, 4- methylbenzothiazole, 5bromobenzothiazole,- 5- acetaminobenzothiazole, 5-iod0bhzbthiziz6le, 5'-

dimethylaminobenzothiazole, 5-methylbenzothia= N zole, S-methoxybenzothiazole 5f ethoxybenzothiazole, 5-phenylbenzothiazole, 6-methylbenzo" thiazole, G-chlorobenzothiazole, 6-methoxybenzothiazole, G-ethoxybenzothiazole, etc), a nucleus of the benzoselenazole series (e. g. benzoselenazol'e', 5-chlorobenzoselenaz'oleg etc), a nueleus of the a-naphthothi'azole series,- a nucleus of the B- naphthothiazole series; a nucleus of the a-naph'- thoxazole series, a nucleus" of the c-naphtho'xazole series, a nucleus of the ii-naph'thoselenazole series, a nucleus of the B-naplithoselenazole series, a nucleus of the thiazoline series, a nucleus of the simple thiazole series (e. g. 4-methylthiazole, 4-phenylthiazole, 4-(2-thienyl) thiazole, etc), a nucleus of the simple selena'zole series (e. g. i-met'hylselenaz'ole, -ph'enylselenazole, etc.) a nucleus of thesimple oxa'zol'e' series (e. g. 4 methyloxazole; -phenyithiazole, etc), a nucleus of the quinoline series (e. g'. quinoline, (i=methylquinoline, fi-meth-oxyquinoline, etc), a nucleus of the pyridine series; a' nucleus of the 3;,3 dialk-ylindolenine series (e. g; 3,3'-dimethylindolenine, etc. etc. H I

In accordance with myinvention; I prepare merocyanine dyes containing a sulfoalkyl or a carboxyalkyl grouponthe nitrogen atom of the auxochromophore group by condensing a cyclam monium carboxyalkyl orsulfoalkyl quaternary salt containing in the acry-position (i. e. one-of so-al led reactive positions) a thioether e. g. an a-lliylthio, an aralkylthio or an arylthio group; or ahalogen atom; e. g.- achlorine, a bromine or an iodine atom, with a heterdcyelic compound containingfrom 5 to 6' atoms iii the heterocyclic ring and containing a ketoinethylene group CO(3H2) inth'e'heteroc'yclicring; i. e. a heterocyclic compound selected from those having the following general formula:

//Q\{ Ha where Q has the value given above. This conden'sation gives simple" m'erocyanine dyes taining on the nitrogen atom of the easternmophore group a carboxyalkyl or a sulfoalkyl group, i. e. merocyanine dyes of the following general formula:

R :.?L:L) C= C/\C=O Where R, L, 11, Q and 2 have the values given above.

The condensations are advantageously carried out in the presence of a basic. condensing agent, e. g. a tertiary amine, such as pyridine, a tri- 4 alkylamine or a N-alkylpiperidine. Alkali metal carbonates or alkali metal alcoholates can also be employed. A reaction medium can be employed, e. g. a lower molecular weight alcohol, such as ethyl, n-propyl, isopropyl, n-butyl or isobutyl alcohol.

Simple merocyanine dyes containing a 4- quinoline nucleus and containing on the nitrogen atom of the auxochromophore group a carboxyalkyl or a sulfoalkyl group can also be prepared by ondeneing a (i'uinoline carboxyalkyl or sulfoalkyl quaternary salt containing no substituent in the 4-position, with a heterocyclic compound containing from 5 to 6 atoms in the heterocyclic ring and containing in the heterocyclic ring a integer of from I to 4 are advantageously employed. H

In. accordance with my invention, I prepare merocyanine dyes of the carbo series (1. e. merocar'bocyanine dyes) containing on the nitrogen atom of the auxochromophore group a carboxyalkyl or a sulfoalkyl group by condensing a. cyciammonium carboxyalkylor sulfoalkyl quaternary salt containing in the aor 7-p0sition (i. e. one of the so-called reactive positions) a fl-alylmninuvinyl group with a heterocyclic compound containingfrom 5 to 6? atoms in the heterocyclic ring and? containing. an intracyclic ketomethylene group, i. e. a heterocyclic compound selected from those having the following general formula:

wherein. Q has the value given above. The fl-arylaminovinyl' group is advantageously an acylated fl-arylaminovinylgroup, e. g. a fl-acetanilidovinyl group. This condensation gives merocarbocyanine dyes containing a carboxyalkyl or sulfoalkyl group on the nitrogen atom of the auxochromophore group, i. e. merocyanine dyes of the following generalformula:

[III 2" wherein R, L, 11, Q and 2 have the values iven W The condensations are advantageously carried outin the presence of a. basic condensing agent, e; g. atertiaryamine, such as a trimethylamine, triethylene, dimethylaniline, or a N-alkylpiperidine. Areactionmedium isadvantageouslyemployed, e. g.- pyridine or a lower molecular weight alcohol, such, as ethyl, n-propyl, isopropyl, n-butyl or isobutyl alcohol. An alkali metal carbosylate in a carboxylic anhydride can also be used as basic condensing agent, e. g. sodium acetate in acetic. anhydride.

The above merocarbocyanine dyes can also be prepared by condensing a cyclammonium carboxyalkylquaternary salt or cyclammonium sulfoalkyl quaternary salt containing in the aor -position (i. e. one of the so-called reactive positions) a CH2R4r group wherein R4 represents a hydrogen atoin or an alkyl group, with an arylaminomethyiene compound of the following general formula:

IV. Ri [/QX i r-n= "cio wherein Q5 has the value given above, Rs repremethylene 3 ethylrhodanine, 5-acetanilido-3-' phenylrhodanine, 5acetanilidomethylene-3-ethy1-2-thio-2,4 3,5) -oxazoledione, 5-acetanilidomethylene 3 ethyl-1-phenyl-2-thiohydantoin, 4 acetanilidomethylene-3-methyl-1-phenyl-5- pyrazolone, 5-acetanilidomethylene-2-diphenylamino-4(5) -thiazolone, etc. The condensations are advantageously carried out in the presence of a basic condensing agent, such as those recited above. A reaction medium of a lower molecular weight alcohol is advantageously employed.

lhe above merocarbocyanine dyes containing a substituent on the dimethine chain adjacent to the keto heterocyclic nucleus can also be prepared by condensing a cyclammonium carboxyalkyl or sulfoalkyl quaternary salt containing in the czor y-position a B-alkylmercaptovinyl group, with a heterocyclic compound containing an intracyclic ketomethylene group and containing from 5 to 6 atoms in the ring. The condensations are advantageously carried out in the presence of a basic condensing agent, e. g. a trialkylamine, a N-alkylpiperidine or an alkali metal carbonate. A reaction medium of a lower molecular weight alcohol is advantageously employed.

In accordance with my invention, I prepare merocyanine dyes of the dicarbo series (i. e. merodicarbocyanine dyes) containing a carboxyalkyl or a sulfoalkyl group on the nitrogen atom of the auxochromophoric group by condensing a cyclammonium carboxyalkyl or sulfoalkyl quaternary salt containing in the aor -position, a 4-arylamino-L3-butadienyl group with a heterocyclic compound containing from 5 to 6 atoms in the heterocyclic ring and containing a ketcan aryiaminoallylidene compound of theiollowing general formula:

" wherein Q has the value given above, R1 represents a member selected from the group consistingof a hydrogen atom and an acyl group (especially acetyl, propionyl or butyryl) and Re represents an aryl group, e. g. phenyl or naphthyl. Typical of 'such arylaminoallylidene compounds are: 5 'y acetanilidoallylidenerhodanine, 5- acetanilidoallylidene 3 ethylrhodanine, 5 'y acetaniloallylidene 3 phenylrhodanine, 5 'y acetanilidoallylidene 3 laurylrhodanine, 5 'y acetanilidoallylidene 3 ethylrhodanine, 5 y acetanilidoallylidene 3 ethyl-2-thio 2,4(3,5)

" oxazoledione, 5-y-a.cetanilidoallylidene-3-ethylmethylene group in the ring. The 4-arylamino- 1,3-butadienyl group is advantageously an acylated 4-arylamino-1,3-butadienyl group, e. g. a 4-acetanilido-1,3-butadienyl group. This condensation gives merodicarbocyanine dyes con- I V taining a carboxyalkyl or sulfoalkyl group on the nitrogen atom of the auxochromophoric group, i. e. merocyanine dyes of the following general formula:

wherein R, L, n, Q and Z have the values given above.

The condensations are advantageously carried out in the presence of a basic condensing agent, e. g. a tertiary amine, such as trimethylamine, triethylamine, dimethylaniline, or a N-alkylpiperidine. A reaction medium is advantageously employed, such as ethyl, n-propyl, isopropyl, n-butyl or isobutyl alcohol. An alkali metal carboxylate in a carboxylic anhydride can also be used as basic condensing agent, e. g. sodium acetate in acetic anhydride.

The above merodicarbocyanine dyes can also be prepared by condensing a cyclammonium carboxyalkyl quaternary salt or a cyclammonium sulfoalkyl quaterary salt containing in the a or sents a hydrogen atom or an alkyl group, with 1-phenyl-Z-thiohydantoin, 5-y-acetanilidoallylidene-1,3-diphenyl-2-thiohydantoin, 5 'y acetanilidoallylidene 2 diphenylamino 4(5) -thiazolone 5 'y acetanilido,- 2 ethylphenylamino-- 4 5) -thiazolone, 4-' -acetanilidoallylidene-1- (2-- benzothiazolyl) 3 methyl 5 pyrazolone, 4'-"y-- acetanilidoallylidene-3-methyl-l-phenyl 5 py-- razolone, etc. These condensations are advanta-- geously carried out in the presence of a basiccondensing agent, e. g. the basic condensing;

agents set forth above under merodicarbocyanine.

dyes.

In accordance with my invention, I prepare: merotricarbocyanine dyes by condensing a eyelammonium carboxyalkyl quaternary salt or cyc-- lammonium sulfoalkyl quaternary salt containing wherein Q has the value given above, R9 represents a member selected from the group consisting of a hydrogen atom and an acyl group (especially acetyl, propionyl or butyryl) and R10 represents an aryl group, e. g. phenyl or naphthyl. Typical of such arylamino-2,4-pentadienylidene compounds are: 5-(5-acetanilido2,4-pentadienylidiene) -3-ethylrhodanine, 5 (5 acetanilido- 2,4-pentadienylidene)-2-thiobarbituric acid, 5- (5-acetanilido-2,4-pentadienylidene) 3 ethyl 2-thio-2,4(3,5) -oxazoledione, 5 (5 acetanilido- 2,4 -pentadienylidene) -1,3-diphenyl 2 thiohydantoin, 5-(5-acetanilido-2,4-pentadienylidene- 2-ethylphenylamino-4 (5) -thiazolone, 4- (5-acetanilido 2,4 pentadienylidene) -3 methyl 1 phenyl-5-pyrazolone, etc. The condensations are advantageously carried out in the presence of a basic condensing agent, e. g. the basic condensing agents set forth above under merodicarbocyanine dyes.

In accordance with my invention, I prepare merocyanine dyes containing more than two heterocyclic nuclei by treating a merocyanine dye of the following general formula:

wherein R, R1, 11., Z, m and Q1 have the values recited above, and d represents a positive integer of from 2 to 3 with an alkyl salt to obtain a quaternary alkylmercapto compound of the following general formula:

yield of purified dye was 1.3 g., 66 per cent. Th dye was a sensitizer for a gelatino-sllver-brw miodide emulsion to 640 mg with maxima at 5-10 and 595 me.

wherein R, L, n, m, R1, Q1 and Z have the values recited above, R2 represents an alcohol radical (i. e. an alkyl group substituted or unsubstituted) d represents a positive integer of from 1 to 2 and X represents an anion. I then condense the quaternary compound with a heterocyclic compound containing 5 to 6 atoms in the heterocyclic ring and containing a ketomethylene group in the heterocyclic ring. This condensation gives complex merocyanine dyes containing three or four heterocyclic nuclei, i. e. merocyanine dyes of the following general formula:

wherein R, L, n, m, Z, Q1, R1, and Q have the values set forth above and d represents a positive integer of from 2 to 3.

The condensations of the quaternary alkylmercapto compounds with the ketomethylene compounds are advantageously carried out in the presence of a basic condensing agent, e. g. a trialkylamine or a N -alkylpiperidine or an alkali metal carbonate, using a lower molecular weight alcohol as reaction medium.

The following examples will serve to illustrate further my new dyes and the manner of obtaining the same.

Example 1.5- (3 ,8-carboxyethyZ-2 (3) -benzothiazolylidene) ethylidenel 3 ethylrhodanine 1.75 g. (1 mol.) of 2-methylbenzothiazole pcarboxyethiodide, 1.5 g. (1 mol.) of.5-acetan'ilidomethylene-3-ethylrhodanine, 1.0 g. (1.m01.) of triethylamineand 25 cc. absolute ethyl-alcohol were refluxed together for minutes. "The crimson solution was cooled .to room temperature, the dye precipitated by adding 5 'cc. o'f20 per cent "HCl and the mixture chilled to 0 C. 'The dye was "collected on a filter, washed with-water and methyl alcohol and dried. The yield of violet crystals was 1.5 g., '76 per cent. "The crude dye was dissolved in 200 cc. 'of hot methyl alcohol containing an excess of 'triethylamine,ifiltered and the acidform of the dyeprecipitated'from the chilled filtrate with excess per cent HCl. The product was filtered off, washed on the filter with water and methyl alcoholand dried. The dye was thus obtained as a purple felt of crystals melting with decomposition at 182-184 C. The

Example 2.--5- (3-carboxymethyl-2G) -benzo.r azolylidene) ethylidene] -3-ethylrhodanine 4.2 g. (1 mol.) of 2-fi-acetanilidovinylbenzox- .azolecarboxymethobromide, 1.6 g. (1 mol.) of .3- ethylrhodanine, 1.0 g. (1 mol.) of triethylamine and 25 cc. absolute ethyl alcohol were refluxed together for 10 minutes. The orange reaction mixture was cooled to room temperature, an excess of 15 per cent HCl added to precipitate the acid form of the dye and the mixture chilled to 0 C. The orange crystals of dye were collected on a filter, washed on the filter with water and methyl alcohol and dried. The yield of crude dye was 2.2 g. (61 per cent.) The dye was purified by dissolving the triethylamine salt in methyl alcohol, filtering and precipitating the acid form of the dye with HCl. The purified ,dye was obtained as vermillion crystals melting with decomposition at 232-234 C. The yield of purified dye was 1.9 g., 53 per cent. The dye sensitized a gelatino-silver-bromiodide emulsion to 600 mil with a maximum at 550 m Example -3.-5- (3-e-carboryethyl-2 (3-benzoa;azolylidene) ethylidenel-3-ethylrhodanine 1.7 g., 45 percent. The product was purifiedby dissolving the triethylamine salt in methyl alcohol, 'filtering and precipitating'the acid form of the dye with HCl. *The yield of m inute. red crystals was'1.5 .g., 40 per cent. The purifieddye melted with decomposition at '21 1 213 C. The

dye-wasa sensitizer for a gelatino-silver-bromiodide emulsion "to "610ma'with a maximum at 9 Example 4.-5- E (3-carbom/methyl-2 (3) -a-naphthothiazolylidene) ethylidene] 3-ethylrhodanine 1.7 g. (1 mol.) of 2-methyl-a-naphthothiazole carboxymethobromide, 1.5 g. (1\ mol.) of 5-acetanilidomethylene-3-ethylrhodanine, 1.0 g. (2 mols.) of triethylamine and 50 cc. of absolute ethyl alcohol were refluxed together for 15 minutes. The purple solution was cooled to room temperature, 5 cc. of 20 per cent HCl added and the mixture chilled to C. The green crystals of the acid form of the dye were collected on a filter, washed with water and methyl alcohol and dried. The yield of crude dye was 1.6 g., 73 per cent. The dye was purified by solution of the triethylamine salt in methyl alcohol, filtration and precipitation of the acid form of the dye with HCl. The purified dye was obtained as green crystals melting with decomposition at 269-272 C. with softening from 240 C. The

yield of purified material was 1.2 g., 54 per cent. The dye sensitized a gelatino-silver-bromiodide emulsion to 660 m with maxima at 540 and Example .--5 (3-fl-carbomyethyl-2 (3) -thiazolinylidene) ethylidene] -3-ethylrhodanine 3.0 g. (1 mol.) of Z-methylthiazoline e-caboxyethiodide, 3.1 g. (1 mol.) of 5-acetanilidomethylene-3-ethylrhodanine, 1.0 g. (1 mol.) of triethylamine and 25 cc. of pyridine were refluxed together for one hour. The orange mixture was cooled to room temperature, poured into 200 cc. cold per cent HCl and chilled to 0 C. The acid form of the dye was thus precipitated as a sticky orange solid. The aqueous solution was decanted off and the residue was recrystallized from 100 cc. absoluteethyl alcohol. The crude dye was obtained as orange crystalsin a yield of .6 g., 18 per cent. After a further recrystallization from methyl alcohol (185 cc. per gram of dye) the product melted at 208-210 C. with decomposition. The yield of purified dye was .4 g., 12 per cent. The dye was a sensitizer for a gelatino-silver-bromiodide emulsion to 565 m with a sharp maximum at 540 me.

Example 6.3 ,B carbozcyethyl-5- (3-carboxy- 6 methyl 2(3)-benzo:razolylidene) ethylidenel l0 4.2 g. (1 mol.) of 243-acetanilidovinylbenzoxazole carboxymethobromide, 2.05 (1 mol.) of 3-p3-carboxyethylrhodanine, 1.0 g. (1 mol.) of triethylamine and 25 cc. absolute ethyl alcohol were refluxed for 15 minutes. The orange mixture was cooled to room temperature and the acid form of the dye precipitated by addition of 5 cc. of per cent HCl. After chilling to 0 C. the dye was filtered off, washed with water and methyl alcohol and dried. The yield of orange crystals was 1.0 g., per cent. The dye was dissolved in 200 cc. methyl alcohol containing excess triethylamine, filtered. and the acid form. of the dye precipitated by adding excess dilute HCl. The purified dye was obtained as orange crystals melting with decomposition at 226-228 C. The yield of purified dye was .4 g., 10 per cent. The dye is a sensitizer for a gelatino-silver-bromiodide emulsion to 600 m with a maximum at 550 m Example 7.4 [(3-p-carboxyethyl-2(3)-benzo thiazolylidene) -ethylidene]-3-methyl-1 phenyZ-S-pyrazolone 2H4GOOH 1.2 g. (1 mol.) of 2-methylbenzothiazole p-carboxyethiodide, 1.1 g. (1 mol.) of 4-acetanilidomethylene-3-methyl-1-phenyl-5-pyrazolone, .6 g. (2 mols.) of triethylamine and 25 cc. of absolute ethyl alcohol were boiled together under reflux for minutes. The pink reaction mixture was cooled to room temperature, diluted to 300 cc. with 10 per cent acetic acid and chilled to 0 C. The red crystals of dye were collected on a filter, washed on the filter with water and dried. The yield was 1.3 g., 96 per cent. After recrystallization from methyl alcohol (500 cc. per gram of dye) the product was obtained as red crystals r which melted with decomposition at 238-240 C.

The yield of purified material was 1.1 g., 82 per cent. The dye is a sensitizer to 520 m for a .gelatino-silver-bromiodide emulsion.

Example 8.-4[ (1 3-carb0xyethyl-3,3-dimethyl- 2(1) -indolylidene) -ethylidene]-3 methyl 1 phenyl-S-pyrazolone N 0 CH) one-0 N-CuHu C=CH-CH= =0 1.2 g. (1 mol.) of 2,3,3-trimethylindolenine-B- carboxyethiodide, 1.1 g. (1 mol.) of 4-acetanilidomethylene-3-methyl-1-phenyl-5-pyrazolone, .6 g. (2 mols.) of triethylamine and 25 cc. of absolute ethyl alcohol were boiled together under reflux for 30 minutes. The reaction mixture was chilled to room temperature, diluted to 300 cc. with 10 per cent acetic acid and chilled to 0" C. The

orange crystals of dye were collected on a filter, washed on the filter with water anddried. The yield of dye was 1.2 g., 87 per cent. After recrys- "tallization from methyl alcohol (66 cc. per gram 'of dye) the product was obtained as yellow needles which melted with decomposition at l56- 11 157 C. The yield of purified dye was..75 g., .54 per cent. The dye did not sensitize a gelatinosilverechloro-bromiodide emulsion.

Example 9. -,5 (3-p-carbomyethyZ-5-chZor0-2- (3) ebenzothiaeolylidene) -1,'3-butadienylidenel rhodanine 5.54 :g. (1 mol.) of 2-(4eacetanilido-L3-butadienyl)-5-chlorobenzothiazole B-carboxyethiodide, 1.33 g. (1 mol.) of rhodanine, 2.0 g. (2 mols.) of .triethylamineandfio cc. of absolute ethyl a1- cohol were boiled together under refiux .for 15 minutes. Crystals of dye separated from the boiling solution. The mixture was chilled to C. and diluted to 300 cc. with 10 per cent acetic acid. The dye was collected on a filter, washed on the filter with methyl alcohol and dried. The yield of dark blue solid was 3.0 g., 71 per cent. For purification the dye was dissolved .in hot methyl alcohol containing an excess .of 'triethylamine beyond that required to form the salt of the dye. The 'hot solution was filtered and the dye precipitated from the cooled solution by addition of acetic acid. The yield of purified dye was 2.6 g., 62 percent. The dye melted at 197-200" C. with decomposition. The-dye had no sensitizing action "in a gelatino silver-bromiodide emulsion. The 2-(4-acetanilido 1,3 butadineyl) chlorobenzothiazole fi-carboxyethiodide used herein was prepared as follows: 38.35 g. of 5-chloro-2-methylbenzothiazole-B-carboxyethi0dide, 25.85 g. (1 mol.-) of 6-anilinoacroleinanilhydrochloride and '1'50 cc. of 'acetic anhydride were boiled together under reflux for 15 minutes. The brown solution was cooled, diluted to 500 cc. with ether and chilled-to 0 C. The ether solution was decanted from the sticky precipitate and the latter was boiled up with 50 cc. of acetone. The acetone solution was chilled with stirring in an ice bath whereupon crystals separated. After standing for 3 hours, the product was collected on a filter, washed 0n the filter with acetoneand dried. The yield of green crystals was 20.4 g., 3'7 per cent.

Example 10.-5-[ (3 epcarb oxyethyl-Z (3) -benzo thzazoZylidenelisopropylidenel-3 =ethylrhodanine 1.4 g. (lmol) of 3-;8-carboxyethyl-2-thioacetylmethylenebenz th-iazoline and .93 g. .(1 mol.) of methylp-taluenesulfonate were heated together on the steam bath for 30 minutes. .8 g. (1 mol.)

.of .3-et.h yl rhodanine, .5 g. (1 mol.) of triethylamine and .25 cc. .of absolute ethyl alcohol were added and the .mixturewas boiled under reflux for 30 minutes. The red reaction mixture was cooled to room temperature, 10 cc..of glacialacetic acid were added and the mixture was chilled to 0 C. The product was collected on a filter, washed on the filter with methyl alcohol and dried. The yield of green crystals was 1.8 g., 88 per cent. The dye was purified by dissolving it in 200 cc. of hot methyl .alcohol containing 2 cc. of triethylamine, filtering the-solutionand precipitating the dye by addition of 5 cc. of glacial acetic acid. The purified dye melted with decomposition at 219- 221 C. The yield of purified material was 1.5 g., '74 percent. The dye sensitized agelatino-silverbromiodide emulsion from 500 to 620 mpwith a maximum at 540111;!

Example '11 .--5-' E (3-,8-carboxyethyZ-2 (3) -benzothiazolylidene) -a-ethylethylidenel '3 ethyl1hodam'ne 1.45 'g. ('1 mol.) of 3-p-carboxyethyl-2-thiopropionylmethylenebenzothiazoline and :9 g. (1 mol.) of methyl p-toluenesulfonate were heated on the steam bath for one hour. The red solid product was washed by decantation with 25 cc.'of ether. .'8 g. ('1.mol.) 'of B-ethylrhodanine, .5 8. (1 mol.) of-triethanolamine and25 cc.:of.absolute ethyl alcohol were added and the mixture boiled under reflux for 15 minutes. The product was isolated and purified in the same manner as Example 1'0. The yield of crude red crystals was 1.4 g., 67 per cent. The purified product melted at 229-230 C. with decomposition. The yield of purified material was 1.3 g., 62 per cent. The dye is a sensitizer in a gelatino-silver-bromiodide emulsion from 500 to 620 m Example 12.5- (3-B-carboxyethyZ-2 (3) -benzothiazoly'lidene) a-ethylethylidcnel-3ethyl-2- thi0-2,4'(3,5) -o:vazoledione 1.45 .g. (1 mol.) of 3-fi-carboxyethyl-2 thiopropionylmethylenebenzothiazoline and .9 g. (1 mol.) of methyl-p-toluenesulfonate were heated on the steam bath for one hour. The red solid product was washed by decantation with 25 cc. of ether. .73 g. (1 mol.) of 3-ethyl-2-thio- 2,4('3,-5)-oxazoledione, .5 g. (1 mol.) of triethylamine and 25 cc. of absolute ethyl alcohol were added and the mixture boiled under reflux for 19 minutes. The product was isolated and purified in the same manner as Example 10. The yield of crude pink crystals was .9 g., 44 per cent. The purified product melted with decomposition .at 226-227 C. The yield of purified material was 6 g., 29 per cent. The dye is a sensitizer for a elatino-silver-bromiodide emulsion from 500 to 5'70 my.

Example 13.--- (1 -carboxymethyl-4 (1 -quinolylidene) ethylidene] -3-ethylrhodanine HQOOOH 2.8 g. (1 mol.) of lepidine carboxymethobromide, 3.1 g. (1 mol.) of 5-acetanilidomethylene-3- ethylrhodanine, 2.0 g. (2 mols.) of triethylamine and 25 cc. of absolute ethyl alcohol were boiled together under reflux for 1 hour. The mixture was cooled to room temperature, cc. of glacial acetic acid added and chilled to 0 C. The dye was collected on a filter, washed on the filter with methyl alcohol and water and dried. The yield of dull blue crystals was 2.4 g., 65 per cent. For purification the dye was dissolved in 50 cc. hot methyl alcohol containing 1 cc. of triethylamine, filtered and precipitated by adding 5 cc. of glacial acetic acid. The yield of purified material was 2.0 g., 54 per cent. The purified dye melted at 1515-197 C. with decomposition. The dye is a sensitizer from 540 to 670 m with a maximum at 650 m in a gelatino-silver-bromiodide emulsion.

Example 1 4.-5- (3-fi-carboxyethyl-2G) -benzothlazoylidene) -ethylidenel-3-ethg1Z-1 phenyl- 2 -thiohydantoin 3.5 g. (1 mol.) of 2-methylbenzothiazole-pcarboxyethiodide, 3.65 g. (1 mol.) of 5-acetanilidomethylene-B-ethyl-l-phenyl-2-thiohydantoin, 2.0 g. (2 mols.) of triethylamine and 25 cc. of absolute ethyl alcohol were boiled together under reflux for 1 hour. The dye was isolated in the same manner as Example 13. The yield of green crystals of crude dye was 3.4 g. '76 per cent. The dye was recrystallized from glacial acetic acid (52 cc. per gram). The yield of purified dye was 2.4 g., 53 per cent. The pure dye melted at 221-223 C. with decomposition. The dye is a sensitizer to 560 m with a maximum at 520 m l in a gelatino-silver-chloro-bromiodide emulsion.

Example 1 5.-5- (3-fi-carbo-xyethyl-2 (3) -benzothiazolylidene) ethylidene] 3 ethyl-Z-thio- 2,4 (3,5) -oxazoledione gHcCO 0H p 3.5 g. (1 mol.) of Z-methylbenzothiazole-fl- :carboxyethiodide, 2.9 g. (1 mol.) of 5-acetanilidomethylene- 3-ethyl-2-thio-2,4(3,5) oxazoledione, 2.0 g. (2 mols.) of triethylamine and 25 cc. of absolute ethyl alcohol were boiled together under reflux f0! 1 hour. The mixture was diluted with 300 cc. of 10 per cent acetic acid and chilled to 0 C. The product was collected on a filter, washed on the filter with alcohol and water and dried. The yield of red crystals was 3.7 g., 98 per cent. The dye was recrystallized from glacial acetic acid (50 cc. per gram). The yield of purified material was 2.0 g., 53 per cent. The pure dye melted at 226-227 C. with decomposition. The dye is a sensitizer from 500 to 630 m with 'a maximum at 550 m in a gelatino-silverbromiodide emulsion.

Example 16.-5-[ (5-chl0ro-3-;8-sulfoethyl-2(3) benzothiazolylidene) -ethylidenel -3 ethylrhodanine triethylamine salt zH4S O aH (C2115);

1.86 g. (1 mol.) of 5-chloro 2-methylbenzothiazole-B-sulfoethylbromide, 1.5 g. (1 mol.) of 5- 'acetanilidomethy1ene-3-ethylrhodanine, 1.0 g. (2

mols.) of triethylamine and 15 cc. of absolute The reaction mixture was cooled, diluted was collected on a filter, washed with absolute ethyl alcohol and dried. The yield of red crystals with a golden reflex was .5 g., 18 per cent.

terial was .3 g., 11 per cent. The dye is a sensitizer in a gelatino-silver-bromiodide emulsion from 500 to 630 mp with maxima at 540 and ,580' my 50 Example 17.5-[ (3-p-carboxyethyl-2G) -benz- 1.0 g. (1 mol.) of 5-[(3-B-carboxyethyl 2(3)- bath at C. for 20 minutes. The red liquid product was cooled, washed by decantation with 50 cc. of ether and the residue dissolved in 25 cc. of pyridine.

.43 g. (1 mol.)v of 3-ethylrhodanine and 1.0 g. (2 mols. plus excess) of triethylamine were added to the pyridine solution and the mixture boiled under reflux for 51minutes. The purple reaction mixture was cooled to room temperature, poured into'500 cc. of 10 per cent acetic acid and chilled to C. The dye was collected on a 'filter, washed on the filter with methyl alcohol and dried. The yield of blue crys-- tals was .8 g., 60 per cent. The dye was recrystallized from glacial acetic acid. (190 cc. per gram.) The purified dye was obtained as dark green crystals which melted at 292-294" C. with decomposition. The yield of purified dye was .5 g.., '3'! per cent. Thedye is a sensitizer from 510 to 600 ru with amaximum at 610 m in a gelatino-sllver-bromiodide emulsion.

Example 18.-- (3-,s-carbozyethyl-2 (3) -benzothiazolylidene) -3-ethylrhodanine 11.35 g. (1 mol.) of 2-phenylmercaptobenzothiazole and 10.0 g. (1 mol.) of B-iodopropionic acid were heated together in a test tube over a gas flame for 3 minutes. The dark brown viscous product was cooled to room temperature. 7.5 g. (1 mol.) of 3-ethylrhodanine, 93.5 g. (2 mols.) of triethylamine and 25 cc. of absolute .ethyl a1- oohol were added and the mixture was boiled with stirring for 5 minutes. The reaction mixture wascooled. poured into 300 cc. of per cent acetic acid and chilled to 0 C. The sticky brown precipitate was stirred with two 300-cc. .portions of cold water and finally boiled up with 100 cc. of methyl alcohol. The alcohol solution was chilled .to 0 C... the dye filtered off and washed on the filter with methyl alcohol. The yield of brown crystals was 3.7 g., 22 per cent. The dye was purified .by dissolving in 150 cc. methyl al- 001101 plus 3 cc. of triethylamine, filtering the solution and precipitating the product by adding excess glacial acetic acid. The yield of brown crystals melting at 254-256 C. with decomposition was 3.0 g., 18 per cent. The dye is a sensitizer to 500 me with a maximum at 470 m in a. gelatino-silver-chlorobromiodide emulsion.

Example 19.5- (3 B-carbomyethyZ-ZQ) -benzoxazolylidene) 2,4 heradienylidenel-1,3-diphenyl-Z-thiobarbituric acid 4.9 g. (11:101.) 0L5-(5-acetanilido-2,4 pentadienylidene) -.1,3 diphenyl 2-thiobarbituric acid, 3.3 g. (1 mol.) of 2-methylbenzoxazole .B-carboxi thiodide, 50 cc. of absolute .ethyl alcohol and 2 g. (2 .mol.) of triethylamine were boiled under reflux for .30 minutes. The reaction mixture was chilled and acidified with dilute (3 per cent) hydrochloric acid, whereupon the dye precipitated. The .dye was filtered off, washed with water, methyl alcohol and dried. Yield 18 per cent. The dye was suspended in warm methyl alcohol and sufilcient triethylamine added to produce a solution of the dye as its triethylamine salt. The triethylamine salt solution was filtered and then acidified with dilute hydrochloric acid, whereupon the dye precipitated. The dye was again taken up in methyl alcohol and triethylamine and again precipitated by acidifying the solution. The dye was washed with methyl alcohol and obtained in 7 per cent yield as dark, almost black crystals, melting at 180 to 182 C. with decomposition. The dye had no sensitizing action on a gelatino-silver-halide emulsion.

Example 20.5-[(3 )3 carboatyethyZ-ZU) -benzoasazolylidene) 1,3 butadienyZidene]-1,3-diethylbarbituric acid 3.35 g. (1 mol.) of 5-'y -acetanilidoallylidene- 1,3-diethylbarituric acid, 3.3 g. (1 mol.) of 2-methylbenzoxazole fi-carboxyethiodide, 25 cc. of absolute ethyl alcohol and 2 g. (2 mol.) of triethylamine were boiled together under reflux for 15 minutes. The reaction mixture was chilled and acidified with 10 per cent acetic acid, whereupon the dye precipitated. The dye was filtered off, washed with methyl alcohol and dried. Yield 12 percent. The dye was suspended in warm methyl alcoholand sufficient triethylamine added to produce a solution of the dye as its triethylamine salt. The triethyla-mine salt solution was filtered and then acidified with 10 per cent acetic acid, whereupon the dye precipitated. The dye was again taken up in methyl alcohol and triethylamine and again precipitated by acidifying the solution. The dye was Washed with methyl alcohol and obtained in 8 per cent yield as minute dark red crystals, melting at 267 to 269 C. with decomposition. The dye had no sensitizing action on a photographic silver halide emulsion.

In the preparation of photographic silver halide emulsions containing the acid merocyanine dyes, it is only necessary to disperse the dyes in the emulsions. Ordinarily this is advantageously accomplished by forming a water-soluble salt of the acid merocyanine dye and dissolving the water-soluble salt in water, methanol or ethanol, or a mixture of water and methanol and ethanol, and dispersing the resulting solution in the emulsion. The salts are advantageously formed by adding to the acid merocyanine dye, wet with a little water, methanol or ethanol, an alkali metal hydroxide, e. g. sodium or potassium hydroxide, or ammonium hydroxide, or an amine, e. g. methylamine, ethylamine, dimethylamine, diethylamine, trimethyiamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, pyridine, N-methylpiperidine, n-propylamine, iso- ,propyl amine, butylamine, p ethoxyethylamine, etc, and taking up the salt which forms in a suitable solvent, e. g. water, methanol, ethanol, a mixture of Water and methanol, a mixture of water and ethanol, etc.

Sensitization by .means of my new acid merocyanine dyes is primarily directed to the ordinarily employed gelatino-silyer-halide developing-out emulsions, e. g. gelatino-silver-chloride, -chlorobromide, -chlorobromiodide, -bromide and bromiodide developing-out emulsions. The acid dyes or their salts are advantageously added to the Washed, finished emulsions and should, of course, be uniformly distributed throughout the emulsion.

The concentration of these compounds in the emulsion can vary widely, e. g, from about 5 to about mg. per liter of flowable emulsion.

atmgoo-uz 1:7 The concentration of-the dye' willivary according to the type of light sensi-tive. material and according to the effects desired. The suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art, upon making the ordinary tests and observations customarily used in the: art of emulsion making. To prepare a gelatino-silver-halide emulsion sensitized'with one of my new dyes, the following-gprocedure is satisfactory: a quantity of the: dyein" salt form I is dissolved in water,

methyl alcohol, ethyl alcohol, a mixture of methyl.- alcohol andrwateror amixture-of ethyl alcoholand water, and a volume of the solution containing from -to'=100"mg; of=dye"is slowlyadded to about 1000 cc. of a gelatino silver-halide emulsion with stirring. Stirring is continued until the dye is uniformly dispersed. With the more powerful of my new-sensitizing dyes, to 50 mg. of dye per 1000 cc. of emulsion suffice to produce the maximum sensitizing effectwith the ordinary gelatino-silver-halide emulsions. The above statements are only'illustrative and are not to be understood as limiting my inventionin: any sense, as' it will be apparent that my' new dyes inthe' art, such; instance, as'by bathing. a plate or film upon which an emulsion is coated, in a solution of the dye' (or its=saltform) in an appropriate-solvent, although such a method is ordinarily. not to'be preferred. The emulsion claims are intended to cover any'combination of these condefising'agentfor each molecular proportion I cyclammonium carboxy'alkyl or sulfoalkyl salt plus one molecular proportion ofbasic condens ing agent'fo'r each 'carboxyl o'rsul'fo'groupv present,

is employed;

The. thioketones, such as 3-B-carboxyethyl- 2* thiopropionylmethylenebenzothiazoline and 3-,B carboxyethyl- 2 thioacetylmethylenebenzm thiazoline, which I'ernploy hereinare described in my. copending. applicationv Serial No. 730,563, now Patent 2,481,698, September 13, 1949, filed of even date. herewith.- The compounds containing an intracyclic lretomethylene group and. a car-- boxyalkyl. or a sulfoalkyl group, e. g. 3-fl-car-- boxyethylrhodanine. which I employ herein: in

practicing my invention are described in the copending application of LeslieG. S. Brooker and;v

FranlcL- White, Serial N0. 605,472, filed July'lfi,

1945 I (now United StatesPatent No. 2,493,747.. dated-January 10,1950) and in thecopendingv application of LeslieaGt S. Brooker and Grafton I-I..Keyes;- Serial No. 605,473yfiled July 16, 1945 (now United States Patent No. 2,493,748, dated: 2-methyl=4-phenylbenzothiazole and quaternary'saltsthereof aredescribed in the copendingapplication of Gertrude- Van January 10', 1950).

Zandt and Leslie G: S. Brooker, Serial No. 709,414;

filed November 13, 1946 (DOWUIiitGd States Patent' can be incorporated by; other methods in many of the photographic emulsions customarily employed 1851" No;- 2,485,679; dated October 25; 1949); 2-"-methyl 5 phenylbenzothiazole and quaternary salts thereof are described in the-jcopending application of Gertrude Van Zandt and Leslie G. S.

Brooker, Serial No. 711,816, filed November 22,

1946, now Patent No. 2,515, 913,.Ju1y 18, 1950.

The cyclammonium sulfoalkyl quaternary salts can be prepared, for example, by heating a heterocyclic nitrogen bas'e" containing a reactive methyl group (i. e. amethylgroup in the a or 'YrPOSi-tlOIl) with a. halogenoalka'nesulfonic acid, ei g. 2-brom'oethanesulforiic acid} 2 -ch'loroethanee; sulfonic acid, p-sulfobenzyl: bromide, etc. In preparing these quaternary salts it is essential to heat at. rather high temperatures .and in the case of -the*halogenoethanesulforfic"acids te'fh'eat for a short time, e:" g. 5to lfirninutes. Temperatures from 160 to 220 C. are advantageously employed. With p-sulfobenzylhalides much longer times of heating can be employed and advantageously are employed." The preparation of typical of these cyclammonium, sulfo'alkyl quaternary salts is further illustrated in the following examples:

Example 21l--5 chloro-z-mefliyllienzothidzolei p-sulfbbenz'ylbromidef Br cmoomsoln 1824 g; (1" moli) of 5-chloro-2-methylbenzothia'zolezand' 25.1; g: (l moli) of pi-sulfobenzylcrystallineychilledto"; 0 C. andfiltered. Thefpr'odiict was washed on: the filter with acetone and dried invacuum: over calcium chloride "yield of gray hygroscopic solid was 921 gr, .31 per" cent. "The- 'p -su'lfobenzyl bromide emplyed above can'be repared as follows; '86-.0 g; '(1' moll)" of p-toluenesulfon'ic acid" and 400's? of bromoform were heatedto C. in an oithath:

The mixture was stirred mechanically while ao'gr 1 mot.) of bromine" was added dropwise overai' period of 30 minutes. The mixture I was 1 heated andstirred 30minutes longer, during 'whiclr'tirne the-color of the bromine disappeared. The-'rnix Example 22.2-methylbeficthiazole p-sulfobenzylbromide Br omornisonsr This-was prepared-as in- Example 21 from 16.4- Y a g. 1' moL), oft2-methylbenzothiazole and 27.6 (1:mol-'.) of: p"-.sultobenzyl bromide The yield of" brownish crystals was 4.8 g., 11 per cent.

This was prepared as in Example 21 from 14.3 g. (1 mol.) of lepidine and 25.1 g. (1 mol.) of p-sulfobenzyl bromide. The yield of yellow crystals was 6.6 g., 17 per cent.

Example 24.-5-chZoro-Z-methylbenzothiazolep-sulfoethylbromide c-cm Cl N Bt C1H4s0lH 18.35.g. (1 mol.) of 5-chloro-2-methylbenzothiazole and 18.9 g. (1 mol.), of 2-bromoethanesulfonic acid were heated over a flame until the temperature of the melt reached 220 C. The temperature was maintained between 200 and 220 C. for 5 minutes, the mixture was cooled, crushed under acetone and chilled to 0 C. The product was collected on a filter, washed on the filter with acetone and dried. The yield of pinkish crystals was 256 g., 69 per cent. The z-bromoethanesulfonic acid employed above can be prepared as follows. 110 g. (1 mol.) of finely powdered sodium 2-bromoethane sulfonate, 200 g. (1 mol. plus 10 per cent excess) of a 10 per cent solution of dry hydrogen chloride in absolute ethyl alcohol and 1000 cc. of absolute ethyl alcohol were stirred mechanically for one hour at room temperature. The precipitated sodium chloride was filtered oil, washed on the filter with absolute ethyl alcohol and the filtrate and washings concentrated as far as possible on the steam bath using the water pump. The mixture was diluted with 500 cc. of dry benzene and again concentrated under reduced pressure. The residue was distilled slowly under as high a vacuum as possible. The product was a heavy oil which solidified to colorless crystals on cooling. The product boiled at 160 to 162 C. at 2 mm.

This was prepared as in Example 21 from 19.9 g. (1 mol.) of 2-methyl-a-naphthothiazole and 18.9 g. (1 mol.) of 2-bromoethane sulfonic acid. The yield of brown crystals was 30.7 g., 79 per cent. 75

20 Example 26.'--2-methylbenzothiazolefi-sulfoethylbromide C- CH;

This was prepared as in Example 21 from 14.9 g. (1 mol.) of 2-methylbenzothiazole and 18.9 g.

(1 mol.) of 2-bromoethane sulfonic acid. The yield of gray crystals was 6.6 g., 20 per cent.

Example 27.-2,3,3-trimethylindoleninefl-sulfoethylbromide C-CH; N

This was prepared as in Example 21 from 15.9 g. (1 mol.) of 2,3,3-trimethylindolenine and 18.0 g. (1 mol.) of 2-bromoethanesulfonic acid. The yield of pink crystals was 16.6 g., 48 per cent.

The cyclammonium carboxyalkyl quaternary salts can be prepared by the methods disclosed 'in the prior art and also by hydrolysis of the corresponding carbalkoxyalkyl compounds. following example illustrates further the preparation of the cyclammonium carboxyalkyl quaternary salts by the hydrolysis of the corresponding cyclammonium carbalkoxyalkyl qua-' ternary salts.

Example 28.Lepidine carboarymethobromide Br CHzCOOH 20.0 g. (1 mol.) of lepidine carbethoxymethobromide and 100 cc. of 48 per cent hydrobromic acid were boiled together under reflux for 30 minutes. to dryness under reduced pressure and the sticky brown product dissolved in 100 cc. of absolute ethyl alcohol. the product collected on a filter and washed on the filter with alcohol. The yield of tan crystals was 13.7 g., per cent.

The cyclammonium carbalkoxyalkyl quaternary salts can be prepared by known methods.

The cyclammonium suli'oalkyl bromides set forth above can be converted to the corresponding iodides by adding to a hot methyl alcoholic solution of the cyclammonium sulfoalkyl bromide a concentrated aqueous solution of potassium iodide. Conversion to the perchlorates can be similarly accomplished by adding to a but methyl alcoholic solution of the cyclammonium sulfoalkyl bromide a concentrated aqueous solution of sodium perchlorate. sulfoalkyl chlorides can be made from the cyclammonium sulfoalkyl bromides by stirring the bromides with a boiling methyl alcoholic suspension of silver chloride, filtering off the silver salts and isolating the cyclammonium sulfoalkyl chloride from the methyl alcoholic solution. cyclammonium sulfoalkyl acetates and thio- The The mixture was concentrated nearly The solution was chilled to 0 C.,

cyclammonium 21 cyanates can-be. sim ilarlyprepared using silver ,aeetate-orsilver thiocyanate; Y

' What I claim as my invention and desire'tdbe secured by Letters Patent .oi'the. United States:

1. The ""merocyanine dyes which are representedzby the following general formula o'=e"- --N-R1 group wherein R2 represents a member selected from the group consisting of an alkyl group and an aryl group, R1 represents a member selected from the group consisting of an alkyl group and an aryl group, at represents a positive integer of from 1 to 2, Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of heterocyclic nuclei of the rhodanine series, the 2-thi0-2,4- (3,5)-oxazoledione series and the z-thiohydantoin series and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of heterocyclic nuclei of the benzoxazole series, the benzothioazole series, the benzoselenazole series, the a-naphthoxazole series, the B-naphthoxazole series, the a-naphthothiazole series, the fl-naphthothiazole series, the a-naphthoselenazole series, the fi-naphthoselenazole series, the thiazoline series, the thiazole series, the seienazole series, the oxazole series, the quinoline series and the 3,3-dialkylindolenine series.

2. The merocyanine dyes which the represented by the following general formula:

/Z\ IQ\ I l R-N-b=(CH-CH)M t =c--c=o Q1 d-l wherein R represents a carboxyalkyl group containing from 1 to 5 carbon atoms, m represents a positive integer of from 1 to 4, Q1 represents a member selected from the group consisting of an oxygen atom, a sulfur atom and a group wherein R2 represents a member selected from the group consisting of an alkyl group and an aryl group, R1 represents a member selected from the group consisting of an alkyl group and an aryl group, d represents a positive integer of from 1 to 2, Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of heterocyclic nuclei of the rhodanine series, the 2-thio-2,l,(3,5)-oxazoledione series and the Z-thiohydantoin series and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group con sisting of heterocyclic nuclei of the benzoxazole series, the benzothiazole series, the benzoselenazole series, the a-naphthoxazole series, the fi-naphthoxazole series, the a-naphthothiazole series, the s-naphthothiazole series, the a-naphthoselenazole series, the p-naphthoselenazole 22 sew;-the?'thiannlihe-.seriwii-therthiuoleiserles, the selenazolm series,- r the quinoline: series and the 3,3-dialkylindolenine series.

3. The 'merocyanine dyes which are; represented by tlieafollow-ingygeneral formula:

, 12;; I AR 1 R-N-C=CHCH=C-C==O wherein R represents a, carboxyalkyl containing, from 1 to -3 carbon atoms, Q represents the non-metallic atoms "necessary to complete a heterocyclic nucleus of the rhodanine series and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series.

4. The merocyanine dye represented by the following formula:

(EHr-CHr-COOH 5. The merocyanine dyes which are represented by the following general formula:

wherein R represents a carboxyalkyl group containing from 1 to 3 carbon atoms and Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the rhodanine series.

6. The merocyanine dye which is represented by the following general formula:

'7. The merocyanine dye which is represented by the following formula:

8. The m'erocyanlne dye which is represented by the following chemical formula:

2,510,001 23 24 -9.'The merocyaninedye which'is'represented REFERENCES CITED i ,fouowing chemical formula? A The following references are of record in the file ptthis patent:

x o, 'UNIZIED STATES PATENTS V Q =G.N,0,HiB -hHu Number Name Date C=CH CH=C/ 5 2,170,803 Brooker Aug. 29, 1999 2,170,804 Brooker I Aug. 29, 1939 N s 9 2,170,805 Brooker Aug. 29,1939 5 H O 10 2,170,806 Brooker Aug. 29, 1939 I 9 H 2,170,807 Brooker; Aug. 29, 1939 "ROBEBTH SPRAQUE- 2,354,524 Kumetat July 25, 1944 'Patent No. 2,519,001

It is hereby certified numbered patent requiring Columns 7 and 8, Formula column 12, line 73,

' 28, after the W0 read SR read 660 my; column 17,

I 19, line 9, for that portion of line 35, for 25 6 g. read 25.6 g.; column 21, line 42, for he and that the sai may conform to Signed and d Letters P the record sealed this Certificate of Correction ROBERT H. that error appears in the printed specification of the above SPRAGUE correction as follows:

for 6 g.

X, extreme right-h Example 23 rea mg atent should be of the case in t 21st day of November, A. D. 1

he Patent read as corrected Office.

August 15, 1950 and portion thereof, for 8H read .6 g.; column 15, line 12, for 600 m rd and comma such, insert for; column after whic read are; above, so that the same THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

1. THE MEROCYANINE DYES WHICH ARE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 